Tri- or tetrasubstituted diphenylphthalides

ABSTRACT

Substituted 3,3-diphenylphthalides, useful as color precursors, particularly in the art of pressure-sensitive duplicating systems and heat-sensitive marking systems, are prepared by condensing substituted 2-benzoylbenzoic acids with substituted anilines.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of our copending applicationSer. No. 527,757, filed Nov. 27, 1974, now U.S. Pat. No. 4,032,527,which is a continuation-in-part of our copending application Ser. No.314,443, filed Dec. 12, 1972.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to substituted 3,3-diphenylphthalides useful ascolor precursors, substituted 2-benzoylbenzoic acids useful asintermediates in preparing them, processes for preparing them, andpressure-sensitive duplicating systems and heat-sensitive markingsystems comprising them.

2. Description of the Prior Art

In the art of pressure-sensitive duplicating systems and heat-sensitivemarking systems color precursors in current use are colorless underneutral or basic conditions, but become colored when contacted with anacidic material such as silica gel, a phenolic resin or an acidic clay.Two known diphenylphthalide color precursors are malachite green lactoneof Formula A, which is described in Beilsteins Handbuch der OrganischenChemie (Vierte Auflage, Band XVIII, Seite 617, 1934), and crystal violetlactone of Formula B, which is described in U.S. Pat. No. 2,417,897(Reissue 23,024). ##STR1##

Two of many patents which describe pressure-sensitive duplicatingsystems containing malachite green lactone and crystal violet lactoneare U.S. Pat. Nos. 2,548,364 and 2,548,365. In such systems malachitegreen lactone and crystal violet lactone, the latter of which is widelyused, produce images whose colors are intense but not deep. Depth ofcolor is desired for easier readability and better xerographiccopiability of the images. In order to overcome lack of color depth,other color precursors have been mixed with crystal violet lactone asdescribed, for example, in U.S. Pat. No. 3,525,630. An unsolved problemin the art has been both intensity and depth of color in the samemolecule. The present invention is a solution to the problem.

PRIOR PUBLICATION

Japanese Application Publication No. 3467, published January 31, 1972(Chemical Abstracts, vol. 77, abstract no. 21580u, p. 122, 1972)describes in English translation a genus of diphenylphthalides ofFormula C wherein R₁, R₂, R₃ and R₄ are alkyl, alkoxy phenyl, β-oxyethylor β-haloethyl, X is inter alia alkyl amino, Y is hydrogen, chlorine orbromine, and n is an integer from 1 through 4 and one species, whosestructural formula is alleged to be Formula D and which is the onlydescribed species of the genus wherein X is alkyl amino (the product ofExample 3). ##STR2##

The present invention was reduced to practice before Jan. 31, 1972, thepublication date of Japanese Application Publication No. 3467. Moreover,it is believed that the product of Example 3 of Japanese ApplicationPublication No. 3467 is not in fact the compound of Formula D, since theproperties thereof do not correspond to the properties of the product ofExample 1B of this application, which has Formula D.

SUMMARY OF THE INVENTION

In its substituted 3,3-diphenylphthalide aspect the invention provides3-(2-X-4-X-phenyl)-3-(2-Y² -4-Y⁴ -phenyl)-4-Z⁴ -5-Z⁵ -6-Z⁶ -7-Z⁷-phthalide of the formula ##STR3## wherein: X is dialkylamino whereinalkyl is non-tertiary alkyl of one to four carbon atoms;

Y² is hydrogen, non-tertiary alkyl of one to four carbon atoms,dialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms, alkanoylamino of two to five carbon atoms, non-tertiary alkoxyone to four carbon atoms or halo;

Y⁴ is the same as Y² when Y² is dialkylamino; or dialkylamino,pyrrolidino, piperidino, morpholino, alkylbenzylamino,alkyl(4-alkoxyphenyl)amino or alkyl(Q-(CH₂)_(n))-amino, wherein alkyl isnon-tertiary alkyl of one to four carbon atoms, alkoxy is non-tertiaryalkoxy of one to four carbon atoms, Q is hydroxy or chloro and n is twoto four when Y² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z⁵ is hydrogen or halo; or non-tertiary alkyl of one to four carbonatoms, nitro, amino or dialkylamino wherein alkyl is non-tertiary alkylof one to four carbon atoms when Z⁴, Z⁶ and Z⁷ are each hydrogen;

Z⁶ is hydrogen or halo; or non-tertiary alkyl of one to four carbonatoms, nitro, amino or dialkylamino wherein alkyl is non-tertiary alkylof one to four carbon atoms when Z⁴, Z⁵ and Z⁷ are each hydrogen; and

Z⁷ is hydrogen or halo.

The compounds of Formula I are useful as color precursors, particularlyin the art of pressure-sensitive duplicating systems and heat-sensitivemarking systems.

In its substituted 2-benzoylbenzoic acid aspect the invention provides2-(2-Y'² -4-Y'³ -benzoyl)-3-Z⁴ -4-Z'⁵ -5-Z'⁶ -6-Z⁷ -benzoic acid of theformula ##STR4## wherein: Y'² is dialkylamino wherein alkyl isnon-tertiary alkyl of one to four carbon atoms, alkanoylamino of two tofive carbon atoms, or non-tertiary alkoxy of one to four carbon atoms;

Y'⁴ is the same as Y'² when Y'² is dialkylamino; or dialkylamino,pyrrolidino, piperidino, morpholino, alkylbenzylamino,alkyl(4-alkoxyphenyl)amino or alkyl-(Q'-(CH₂)_(n))amino, wherein alkylis non-tertiary alkyl of one to four carbon atoms, alkoxy isnon-tertiary alkoxy of one to four carbon atoms, Q' is chloro and n istwo to four when Y'² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z'⁵ is hydrogen or halo; or dialkylamino wherein alkyl is non-tertiaryalkyl of one to four carbon atoms when Z⁴, Z'⁶ and Z⁷ are each hydrogen;

Z'⁶ is hydrogen or halo; or dialkylamino wherein alkyl is non-tertiaryalkyl of one to four carbon atoms when Z⁴, Z'⁵ and Z⁷ are each hydrogen;

Z⁷ is hydrogen or halo

and acid addition salts thereof.

The compounds of Formula II are useful as intermediates in the followingprocesses for preparing compounds of Formula I.

In one of its process aspects the invention provides the process forpreparing 3-(2-X-4-X-phenyl)-3-(2-Y² -4-Y'⁴ -phenyl)-4-Z⁴ -5-Z"⁵ -6-Z"⁶-7-Z⁷ -phthalide of the formula ##STR5## which comprises condensing2-(2-Y² -4-Y'⁴ -benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of theformula ##STR6## with 1-X-3-X-benzene of the formula ##STR7## in contactwith the anhydride of an alkanoic acid of two to five carbon atoms,phosphorus oxychloride or thionyl chloride, wherein:

X is dialkylamino wherein alkyl is non-tertiary alkyl of one to fourcarbon atoms;

Y² is hydrogen, non-tertiary alkyl of one to four carbon atoms,dialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms, alkanoylamino of two to five carbon atoms, non-tertiary alkoxy ofone to four carbon atoms or halo;

Y'⁴ is the same as Y² when Y² is dialkylamino; or dialkylamino,pyrrolidino, piperidino, morpholino, alkylbenzylamino,alkyl(4-alkoxyphenyl)amino or alkyl-(Q'-(CH₂)_(n))amino, wherein alkylis non-tertiary alkyl of one to four carbon atoms, alkoxy isnon-tertiary alkoxy of one to four carbon atoms, Q' is chloro and n istwo to four when Y² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z"⁵ is hydrogen or halo; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms when Z⁴, Z"⁶ and Z⁷ are each hydrogen;

Z"⁶ is hydrogen or halo; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms when Z⁴, Z"⁵ and Z⁷ are each hydrogen; and

Z⁷ is hydrogen or halo.

In its other process aspect the invention provides the process forpreparing 3-(2-X-4-X-phenyl)-3-(2-Y² -4-Y'⁴ -phenyl)-4-Z⁴ -5-Z"⁵ -6-Z"⁶-7-Z⁷ -phthalide of Formula III which comprises condensing2-(2-X-4-X-benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of theformula ##STR8## with 1-Y² -3-Y'⁴ -benzene of the formula ##STR9## incontact with the anhydride of an alkanoic acid of two to five carbonatoms, phosphorus oxychloride or thionyl chloride, wherein:

X is dialkylamino wherein alkyl is non-tertiary alkyl of one to fourcarbon atoms;

Y² is hydrogen, non-tertiary alkyl of one to four carbon atoms,dialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms, alkanoylamino of two to five carbon atoms, non-tertiary alkoxy ofone to four carbon atoms or halo;

Y'⁴ is the same as Y² when Y² is dialkylamino; or dialkylamino,pyrrolidino, piperidino, morpholino, alkylbenzylamino,alkyl(4-alkoxyphenyl)amino or alkyl-(Q'-(CH₂)_(n))amino, wherein alkylis non-tertiary alkyl of one to four carbon atoms, alkoxy isnon-tertiary alkoxy of one to four carbon atoms, Q' is chloro and n istwo to four when Y² is other than dialkylamino;

Z⁴ is hydrogen or halo;

Z"⁵ is hydrogen or halo; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms when Z⁴, Z"⁶ and Z⁷ are each hydrogen;

Z"⁶ is hydrogen or halo; or non-tertiary alkyl of one to four carbonatoms, nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one tofour carbon atoms when Z⁴, Z"⁵ and Z⁷ are each hydrogen; and

Z⁷ is hydrogen or halo.

The foregoing two process aspects of the invention do not providedirectly the compounds of Formula I wherein Y⁴ isalkyl(Q-(CH₂)_(n))amino wherein Q is hydroxy. However, such compoundsare provided by carrying out either of the process aspects of theinvention with the appropriate intermediates wherein Q is hydroxy andthe anhydride of an alkanoic acid of two to five carbon atoms as thecondensing agent, and dealkanoylating the resulting product wherein Q isthe corresponding alkanoyloxy of two to five carbon atoms.

Nor do the foregoing two process aspects of the invention providedirectly the compounds of Formula I wherein Z⁵ or Z⁶ is amino. However,such compounds are provided by carrying out either of the processaspects of the invention with the appropriate intermediates wherein Z⁵and Z⁶ is amino and, if the anhydride of an alkanoic acid of two to fivecarbon atoms is used as the condensing agent, dealkanoylating theresulting product wherein Z⁵ or Z⁶ is the corresponding alkanoylamino oftwo to five carbon atoms.

In one of its system aspects the invention provides a pressure-sensitiveduplicating system comprising a support sheet having a coat ofpressure-rupturable carboxymethylcellulose-gelatin microcapsulescontaining an oil solution of a compound of Formula I.

In its other system aspect the invention provides a heat-sensitivemarking system comprising a support sheet having a coat of a mixture ofa polyvinyl alcohol dispersion of a phenolic material and a polyvinylalcohol dispersion of a compound of Formula I.

DETAILED DESCRIPTION OF THE INVENTION Definitions

Non-tertiary alkyl of one to four carbon atoms is methyl, ethyl, propyl,isopropyl, butyl, isobutyl or sec-butyl.

Alkanoylamino of two to five carbon atoms is acetamido, propionamido,butyrylamino, isobutyrylamino, valerylamino, isovalerylamino,α-methylbutyrylamino or pivaloylamino.

Non-tertiary alkoxy of one to four carbon atoms is methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

Halo is fluoro, chloro, bromo or iodo.

The anhydrides of alkanoic acids of two to five carbon atoms are aceticanhydride, propionic anhydride, butyric anhydride, isobutyric anhydride,valeric anhydride, isovaleric anhydride, α-methylbutyric anhydride andpivalic anhydride.

Preparation of Final Products

In carrying out the processes of the invention a mixture of 2-(2-Y²-4-Y'⁴ -benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of Formula IVand 1-X-3-X-benzene of Formula V or a mixture of2-(2-X-4-X-benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoic acid of Formula VIand 1-Y² -3-Y'⁴ -benzene of Formula VII and the anhydride of an alkanoicanhydride, preferably acetic anhydride, phosphorus oxychloride orthionyl chloride with or without an inert diluent, is heated at atemperature in the range of 30°-150° C. In some cases the product ofFormula III precipitates from the resulting mixture and may be isolateddirectly. Otherwise the resulting mixture is first acidified with adilute aqueous mineral acid, for example, hydrochloric acid, and thenbasified, for example, with dilute aqueous sodium hydroxide, and theproduct is then isolated.

The compounds of Formula I wherein Z⁵ or Z⁶ is amino are alternativelyprovided by reduction of the corresponding compounds of Formula Iwherein Z⁵ or Z⁶ is nitro with, for example, stannous chloride.

The compounds of Formula I wherein Z⁵ or Z⁶ is nitro are alternativelyprovided by nitration of the corresponding compounds of Formula Iwherein Z⁵ and Z⁶ are hydrogen with, for example, a mixture of nitricacid and sulfuric acid. The nitration can produce the 5-nitro isomer,the 6-nitro isomer or a mixture of both.

The compounds of Formula I wherein Z⁵ or Z⁶ is halo are alternativelyprovided by halogenation of the diazonium salts derived from thecorresponding compounds of Formula I wherein Z⁵ or Z⁶ is amino with, forexample, fluoroboric acid, cuprous chloride, cuprous bromide orpotassium iodide.

Preparation of Intermediates

The compounds of Formula IV and Formula VI, which include among them thecompounds of Formula II, are prepared by condensing the corresponding3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -phthalic anhydrides of the formula ##STR10##with the corresponding 1-Y² -3-Y'⁴ -benzenes of Formula VII or1-X-3-X-benzenes of Formula V, respectively, in contact with a Lewisacid, for example, aluminum chloride or zinc chloride, and with adiluent, for example, benzene, chlorobenzene or o-dichlorobenzene, at atemperature in the range of 20°-200° C. This condensation can produceisomers or mixtures of isomers when the Z"⁵ or Z"⁶ substituent of thecompounds of Formula VIII is alkyl, nitro, dialkylamino or halo. Thusthe derived compounds of Formula IV and Formula VI have the substituentat the 4-position or the 5-position. Compounds of Formula IV or FormulaVI having the substituent in the 4-position or the 5-position producethe corresponding compounds of Formula I having the substituent in the5-position or the 6-position.

Acid addition salts of the compounds of Formula II, Formula IV andFormula VI can be prepared with inorganic (mineral) or organic acids. Ifinorganic, the acid can be, for example, hydrochloric acid, hydrobromicacid, nitric acid, phosphoric acid, sulfuric acid or sulfamic acid. Iforganic, the acid can be, for example, acetic acid, glycolic acid,lactic acid, quinic acid, hydrocinnamic acid, succinic acid, tartaricacid, citric acid, methanesulfonic acid or benzenesulfonic acid.

The molecular structures of the compounds of Formula I, Formula II,Formula IV and Formula VI follow from the structures of the compounds ofFormula V, Formula VII and Formula VIII and the synthetic method and maybe identified and corroborated by observation of one or more of thefollowing physical properties: color, melting point (m.p.), solubilitybehavior, acid-base behavior, thin layer chromatographic spectrum,infrared spectrum, mass spectrum, nuclear magnetic resonance spectrumand ultraviolet spectrum.

The compounds of Formula VIII wherein Z⁴ is halo and Z"⁵ or Z"⁶ is nitroor halo are known. Some of the compounds of Formula VIII wherein Z"⁵ orZ"⁶ is dialkylamino are also known. Those which are not known can beprepared, for example, according to the method of U.S. Pat. No.2,597,965 starting with diethyl 4-aminophthalate and, successively,appropriately N-alkylating, de-ethylating and cyclizing.

Some of the compounds of Formula V and the compounds of Formula VIIwherein Y² is dialkylamino are known. These which are not known can beprepared, for example, by appropriately N-alkylating m-phenylenediamine.

Some of the compounds of Formula VII wherein Y² is hydrogen are known.Those which are not known can be prepared by appropriately N-alkylatinganiline. Julolidine is known.

Some of the compounds of Formula VII wherein Y² is alkyl are known.Those which are not known can be prepared, for example, starting withthe appropriate alkylbenzene and, successively, 4-nitrating, reducingthe nitro to amino, N-acetylating, 3-nitrating, deacetylating,deaminating, reducing the nitro to amino and appropriately N-alkylating.

Some of the compounds of Formula VII wherein Y² is alkanoylamino areknown. Those which are not known can be prepared, for example, startingwith m-nitroaniline and, successively, N-alkanoylating, reducing thenitro to amino and appropriately N-alkylating.

Some of the compounds of Formula VII wherein Y² is alkoxy are known.Those which are not known can be prepared, for example, starting withm-hydroxyacetanilide and, successively, appropriately O-alkylating,deacetylating and appropriately N-alkylating.

The foregoing methods also provide the corresponding compounds ofFormula VII wherein Y'⁴ is alkyl(hydroxy-(CH₂)_(n))-amino which are notknown.

Preparation of Systems

Preparation of pressure-sensitive duplicating systems bycarboxymethylcellulose-gelatin microencapsulation of the compounds ofFormula I is accomplished by the method described in U.S. Pat. No.3,649,649. A preferred oil for dissolving the color precursor isisopropylbiphenyl. Preparation of heat-sensitive marking systems bypolyvinyl alcohol dispersion of the compounds of Formula I isaccomplished by the method described in U.S. Pat. No. 3,539,375. Apreferred phenolic material is bisphenol A.

Examples

example 1

a. a mixture of phthalic anhydride (30 g.), N,N-dimethylaniline (60.5g.), aluminum chloride (60 g.) and chlorobenzene (180 g.) was heated (to75° C.) during one hour, then cooled. Ice (50 ml.) was added, thechlorobenzene layer was separated and the chlorobenzene was steamdistilled. Addition of base to a solution of the residue in dilutesulfuric acid afforded 2-(4-dimethylamino)benzoyl)benzoic acid (IV: Y² ═Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ H, Y'⁴ ═ (CH₃)₂ N).

B. A mixture of 2-(4-dimethylamino)benzoyl)benzoic acid (26.8 g.),N,N,N',N'-tetramethyl-m-phenylenediamine (16.4 g.) and acetic anhydride(80 g.) was heated (to 95° C.) during one hour, cooled and poured intodilute hydrochloric acid. The resulting mixture was basified.Recrystallization of the resulting solid from a mixture of toluene andhexane afforded3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)-phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (m.p. 190°-194° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)phthalideformed a gray-black image which was xerographically copiable.

C. Substituting N,N,N',N'-tetra(sec-butyl)-m-phenylenediamine (preparedby N-alkylating m-phenylenediamine with sec-butyl bromide) forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example,there is obtained3-(2,4-bis(di-sec-butylamino)phenyl)-3-(4-dimethylamino)phenyl)phthalide (I: X ═ (CH₃ CH₂ (CH₃)CH)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═H, Y⁴ ═ (CH₃)₂ N).

D. Condensation of 2-(2,4-bis(dimethylamino)benzoyl)-benzoic acid andN,N-dimethylaniline in the presence of acetic anhydride also afforded3-(2,4-bis(dimethylamino)-phenyl)-3-(4-(dimethylamino)phenyl)phthalide.

EXAMPLE 2

A. A mixture of phthalic anhydride (60 g.), N,N-diethyl-m-toluidine(162.8 g.), aluminum chloride (120 g.) and chlorobenzene (360 ml.) washeated (75°-95° C.) during one and one-half hours, then diluted withwater (200 ml., then more). More chlorobenzene (200 ml.) was added andthe chlorobenzene layer was separated and steam distilled. Addition ofsodium hydroxide solution (10% to a solution of the residue in dilutesulfuric acid (20%, 250 ml.) afforded2-(2-methyl-4-(diethylamino)benzoyl)benzoic acid (IV: Y² ═ CH₃, Y'⁴ ═(CH₃ CH₂)₂ N, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ H).

B. A mixture of 2-(2-methyl-4-(diethylamino)benzoyl)-benzoic acid (25g.), N,N,N',N'-tetramethyl-m-phenylenediamine (13.2 g.) and aceticanhydride (75 g.) was heated (to 95° C.) during 1 hour, then refluxedwith dilute hydrochloric acid (32 g. concentrated hydrochloric acid plus160 ml. water) during one and one-half hours. The resulting mixture waspoured onto ice and the pH was adjusted to 6 with sodium hydroxide.Recrystallization of the resulting product afforded3-(2,4-bis(dimethylamino)-phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) ina first crop from toluene (m.p. 204°-206° C.) and in a second crop froma mixture of toluene and hexane (m.p. 191°-195° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)-phenyl)3-(2-methyl-4-(diethylamino)phenyl)phthalideformed a violet-gray image which was xerographically copiable.

C. Substituting m-butyl-N,N-dimethylaniline (prepared by N-methylatingm-butylaniline with dimethyl sulfate) for N,N-diethyl-m-toluidine inpart A of this example, there is obtained2-(2-butyl-4-(dimethylamino)benzoyl)benzoic acid (IV: Y² ═ CH₃ CH₂ CH₂CH₂, Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ H).

D. Substituting 2-(2-butyl-4-(dimethylamino)benzoyl)-benzoic acid for2-(2-methyl-4-(diethylamino)benzoyl)benzoic acid in part B of thisexample, there is obtained3-(2,4-bis(dimethylamino)phenyl)-3-(2-butyl-4-(dimethylamino)-phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ CH₃ CH₂ CH₂ CH₂, HZ⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H).

E. Condensation of 2-(2,4-bis(dimethylamino)benzoyl)-benzoic acid andN,N-diethyl-m-toluidine in the presence of acetic anhydride alsoafforded3-(2,4-bis(dimethylamino)-phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide.

EXAMPLE 3

A. A mixture of phthalic anhydride (5.92 g.),N,N,N',N'-tetramethyl-m-phenylenediamine (6.56 g.), zinc chloride (5.40g.) and chlorobenzene (70 ml.) was heated under reflux for three hours.The chlorobenzene was decanted and the residue was air-dried. A solutionof the residue in dilute hydrochloric acid (10%, 20 ml. plus 20 ml. ofwater) was diluted with more water (20 ml.), affording2-(2,4-bis-(dimethylamino)benzoyl)benzoic acid (II: Y'² ═ Y'⁴ ═ (CH₃)₂N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H) dihydrochloride trihydrate (4 g., m.p.136°-141° C.; after recrystallization from ethanol, m.p. 140°-141° C.).In another preparation the free base (m.p. 165°-168° C.) was obtainedunder less acidic conditions (pH 4-6).

B. A mixture of crude 2-(2,4-bis(dimethylamino)-benzoyl)benzoic acid (7g.), N,N,N',N'-tetramethyl-m-phenylenediamine (1.64 g.) and aceticanhydride was warmed (at 25°-35° C.) during two to three hours, thenpoured into dilute hydrochloric acid (10%). The resulting mixture wasbasified and filtered with a filter aid. The filter cake was extractedwith hot toluene. Dilution of the toluene extract with hexane afforded3,3-bis(2,4-bis(dimethylamino)-phenyl)phthalide (I: X ═ Y² ═ Y⁴ ═ (CH₃)₂N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (m.p. 186°-188° C.).

When applied to silica gel or standard field resin3,3-bis(2,4-dimethylamino)phenyl)phthalide formed a red-brown imagewhich was xerographically copiable.

C. Substituting N,N,N',N'-tetra(sec-butyl)-m-phenylenediamine forN,N,N',N'-tetramethyl-m-phenylenediamine in part A of this example,there is obtained 2-(2,4-bis(di-sec-butylamino)benzoyl)benzoic acid (II:Y'² ═ Y'⁴ ═ (CH₃ CH₂ (CH₃)CH)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H).

D. Substituting N,N-diethyl-m-toluidine forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example,there is obtained3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide,the compound of part B of Example 2.

E. Substituting N-phenylpyrrolidine, N-phenylpiperidine orN-ethyl-N-(3-chloropropyl)aniline forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example,there are obtained, respectively,3-(2,4-bis(dimethylamino)-phenyl)-3-(4-pyrrolidinophenyl)phthalide (I: X═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Y⁷ ═ H, ##STR11##3-(2,4-bis-(dimethylamino)phenyl)-3-(4-piperidinophenyl)phthalide (I: X═ (CH₃)₂ N, Y² ═ Y⁴ ═ Y⁵ ═ Y⁶ ═ Y⁷ ═ H, ##STR12## and3-(2,4-bis(dimethylamino)phenyl)-3-(4-(ethyl(3-chloropropyl)amino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H, Y⁴ ═ CH₃ CH₂ (Cl(CH₂)₂)N).

EXAMPLE 4

A. A mixture of 2-(2,4-bis(dimethylamino)benzoyl)-benzoic acid (2.4 g.),m-(dimethylamino)acetanilide (1.42 g.) and acetic anhydride (20 ml.) wasstirred at room temperature during 2 hours, filtered, diluted withdilute hydrochloric acid (10%) and made alkaline. Recrystallization ofpart of the resulting produce from a mixture of toluene, ligroin andhexane and part from a mixture of ethyl acetate and hexane afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-acetamido-4-(dimethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ CH₃ CONH, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (m.p.97°-136° C.).

When applied to standard field resin3-(2,4-bis-(dimethylamino)phenyl)-3-(acetamido-4-(dimethylamino)-phenyl)phthalideformed a red-blue-brown image which was xerographically copiable.

B. Substituting m-(dimethylamino)-2,2-dimethylpropionanilide (preparedby N-alkanoylating N,N-dimethylphenylenediamine with pivaloyl chloride)for m-(dimethylamino)acetanilide in part A of this example, there isobtained3-(2,4-bis(dimethylamino)phenyl)-3-(2-pivaloylamino-4-(dimethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ (CH₃)₃ CCONH, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H).

C. Condensation of phthalic anhydride and m-(dimethylamino)acetanilideby the method of part A of Example 1 affords2-(2-acetamido-4-(dimethylamino)benzoyl)benzoic acid (II: Y'² ═ CH₃CONH, Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H).

D. Condensation of 2-(2-acetamido-4-(dimethylamino)-benzoyl)benzoic acidand N,N,N',N'-tetramethyl-m-phenylenediamine by the method of part B ofExample 1 affords3-(2,4-bis(dimethylamino)phenyl)-3-(2-acetamido-4-(dimethylamino)-phenyl)phthalide,the compound of part A of this example.

EXAMPLE 5

A. A mixture of phthalic anhydride (15 g.), m-ethoxy-N,N-diethylaniline(19 g.), aluminum chloride (15 g.) and o-dichlorobenzene (90 g.) washeated (to 75° C.) during 1 hour, then diluted with ice-water. Theo-dichlorobenzene layer was separated and steam distilled. Adjustment topH 5 of a solution of the residue in dilute sulfuric acid (10%, 100 ml.)afforded 2-(2-ethoxy-4-(diethylamino)benzoyl)-benzoic acid (II: Y'² ═CH₃ CH₂ O, Y'⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H) (11 g., m.p.174°-181° C.).

B. A mixture of 2-(2-ethoxy-4-(diethylamino)benzoyl)-benzoic acid (6.82g.), N,N,N',N'-tetramethyl-m-phenylenediamine (2.80 g.) and aceticanhydride (20 g.) was heated (70°-75° C.) during one hour, let standovernight and poured into dilute hydrochloric acid. The resultingmixture was basified. Recrystallization of the resulting red precipitatefrom hexane followed by slurrying in alkaline water afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-ethoxy-4-(diethylamino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃ CH₂ O, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═H) (m.p. 146°-150° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(2-ethoxy-4-(diethylamino)phenyl)phthalideformed a blue-black image which was xerographically copiable.

C. Substituting m-isobutoxy-N,N-dimethylaniline (prepared byO-alkylating m-hydroxyacetanilide with isobutyl bromide, thendeacetylating the resulting m-isobutoxyacetanilide, then N-alkylatingthe resulting m-isobutoxyaniline with methyl sulfate) form-ethoxy-N,N-diethylaniline in part A of this example, there is obtained2-(2-isobutoxy-4-(dimethylamino)benzoyl)benzoic acid (II: Y'² ═ (CH₃)₂CHCH₂ O, Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H).

D. Substituting 2-(2-isobutoxy-4-(dimethylamino)benzoyl)benzoic acid for2-(2-ethoxy-4-(diethylamino)benzoyl)benzoic acid in part B of thisexample, there is obtained3-(2,4-bis(dimethylamino)phenyl)-3-(2-isobutoxy-4-(dimethylamino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ (CH₃)₂ CHCH₂ O, Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷═ H).

E. Condensation of phthalic anhydride and N-(m-anisyl)pyrrolidine(prepared from m-anisidine and 1,4-dibromobutane),N-(m-anisyl)piperidine (prepared from m-anisidine and1,5-dibromopentane) or N-methyl-N-(2-chloroethyl)-m-anisidine (preparedfrom N-methyl-m-anisine and 1-bromo-2-chloroethane) by the method ofpart A of Example 1 affords, respectively,2-(2-methoxy-4-pyrrolidinobenzoyl)benzoic acid (II: Y'² ═ CH₃ O,##STR13## Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H),2-(2-methoxy-4-piperidinobenzoyl)benzoic acid (II: Y'² ═ CH₃ O,##STR14## Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H) and2-(2-methoxy-4-(methyl(2-chloroethyl)amino)benzoyl)benzoic acid (II: Y'²═ CH₃ O, Y'⁴ ═ CH₃ (ClCH₂ CH₂)N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z'⁷ ═ H).

F. Condensation of 2-(2-methoxy-4-pyrrolidinobenzoyl)benzoic acid,2-(2-methoxy-4-piperidinobenzoyl)benzoic acid or2-(2-methoxy-4-(methyl(2-chloroethyl)amino)benzoyl)benzoic acid withN,N,N',N'-tetramethyl-m-phenylenediamine by the method of part B ofExample 1 affords, respectively,3-(2,4-bis(dimethylamino)phenyl)-3-(2-methoxy-4-pyrrolidinophenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃ O, ##STR15## Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H),3-(2,4-bis(dimethylamino)phenyl)-3-(2-methoxy-4-piperidinophenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃ O, ##STR16## Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) and3-(2,4-bis(dimethylamino)phenyl)-3-(2-methoxy-4-(methyl(2-chloroethyl)amino)phenyl)phthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃ O, Y⁴ ═ CH₃ (ClCH₂ CH₂)N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═H).

EXAMPLE 6

A. A mixture of tetrachlorophthalic anhydride (21.4 g.),N,N-diethyl-m-toluidine (41 g.), aluminum chloride (30 g.) ando-dichlorobenzene (90 ml.) was heated (75°-95° C.) during one to twohours, then diluted with ice-water. The o-dichlorobenzene layer wasseparated and steam distilled. The residue was heated with dilutesulfuric acid. The mixture was poured onto ice and made alkaline. Theresulting oil was heated in concentrated sulfuric acid. Dilution withwater and purification of the product with toluene and hexane afforded2-(2-methyl-4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid(IV: Y² ═ CH₃, Y'⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ Cl) (26 g.,m.p. 117° C. with sublimation).

B. A mixture of2-(2-methyl-4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid(22.4 g.), N,N,N,',N'-tetramethyl-m-phenylenediamine (8.20 g.) andacetic anhydride (75 g.) was heated (to 95° C.) during one to two hours,then refluxed with dilute hydrochloric acid (32 g. concentratedhydrochloric acid plus 160 ml. water) during one and one-half hours. Theresulting mixture was poured into water and the pH was adjusted.Recrystallation of the resulting product from toluene afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-4,5,6,7-tetrachlorophthalide(I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl)(m.p. 236-238° C.; after slurrying in acetone, 237°-239° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-4,5,6,7-tetrachlorophthalideformed an image which was xerographically copiable.

EXAMPLE 7

A. A mixture of tetrachlorophthalic anhydride (1.92 g.),N,N,N',N'-tetramethyl-m-phenylenediamine (1.64 g.), zinc chloride (1.35g.) and chlorobenzene (40-45 ml.) was heated under reflux during threehours. The chlorobezene layer was decanted and the residue was slurriedwith dilute hydrochloric acid (10%, 20 ml.) and water (20 ml.),affording 2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoicacid (II: Y'² ═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ Cl) (m.p.199°-201° C.).

B. A mixture of most of the2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid frompart A of this example, N,N,N',N'-tetramethyl-m-phenylenediamine (0.82g. plus 0.4 g.) and acetic anhydride was heated under reflux.Concentration of a toluene extract of the resulting product gave a tar,which was slurried in hexane, affording3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetrachlorophthalide (I: X═ Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl) (m.p. 195°-197° C.).

When applied to acidic clay3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetrachlorophthalideformed a red-blue image which was xerographically copiable.

C. Substituting tetrafluorophthalic anhydride, tetrabromophthalicanhydride or tetraiodophthalic anhydride for tetrachlorophthalicanhydride in part A of this example, there are obtained, respectively,2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrafluorobenzoic acid (II:Y'² ═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ F),2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrabromobenzoic acid (II: Y²═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ Br) and2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetraiodobenzoic acid (II: Y'²═ Y'⁴ ═ (CH₃)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z'⁷ ═ I).

D. Substituting2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrafluorobenzoic acid,2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrabromobenzoic acid or2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetraiodobenzoic acid for2-(2,4-bis(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid inpart B of this example, there are obtained, respectively,3,3-bis(2,4-bis(dimethylamino)phenyl-4,5,6,7-tetrafluorophthalide (I: X═ Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ F),3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetrabromophthalide (I: X═ Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Br) and3,3-bis(2,4-bis(dimethylamino)phenyl)-4,5,6,7-tetraiodophthalide (I: X ═Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ I).

EXAMPLE 8

Three portions of a mixture of concentrated nitric acid (0.6 ml. eachportion) and concentrated sulfuric acid (0.66 ml. each portion) wereadded to a mixture of3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)phthalide4.17 g.) and concentrated sulfuric acid (20 ml.) with cooling. Aftereach addition the temperature was allowed to rise to room temperature.The resulting mixture was poured onto ice and the resulting mixture wasbasified, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-5 or6-nitrophthalide (I: ═ Y⁴ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁷ ═ H, Z⁵ or Z⁶ ═ O₂ Nand the other of Z⁵ or Z⁶ ═ H) or a mixture of both.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl)-3-(4-dimethylamino)phenyl)-5 or6-nitrophthalide formed a gray-black image which was xerographicallycopiable.

EXAMPLE 9

In a manner similar to that of Example 8 nitration of3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide(4.57 g.) afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-diethylamino)phenyl)-5 or6-nitrophthalide (I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁷═ H, Z⁵ or Z⁶ ═ O₂ N and the other of Z⁵ or Z⁶ ═ H) or a mixture ofboth.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-5or 6-nitrophthalide formed a gray-black image which was xerographicallycopiable.

EXAMPLE 10

A. Stannous chloride dihydrate (6.7 g.) was added slowly to a mixture ofmost of the product of Example 8 and concentrated hydrochloric acid (50ml.) with heating (60° C.). After 1 hour the resulting mixture wascooled, made alkaline and filtered, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-5 or6-aminophthalide (I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁷ ═ H, Z⁵ or Z⁶ ═ H₂N and the other of Z⁵ or Z⁶ ═ H) or a mixture of both.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl-3-(4-dimethylamino)phenyl)-5 or6-aminophthalide formed a gray-violet or gray-brown image which wasxerographically copiable.

B. Condensation of 4-aminophthalic anhydride andN,N,N',N'-tetramethyl-m-phenylenediamine by the method of part A ofExample 3 affords 2-(2,4-bis(dimethylamino)benzoyl)5-aminobenzoic acid.

C. Condensation of 2-(2,4-bis(dimethylamino)benzoyl)-5-aminobenzoic acidand N,N,N',N'-tetramethyl-m-phenylenediamine by the method of part B ofExample 3 and deacetylation of the resulting product affords3,3-(2,4-bis(dimethylamino)phenyl-6-aminophthalide (I: X ═ Y² ═ Y⁴ ═(CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ H₂ N).

EXAMPLE 11

In a manner similar to that of Example 10 reduction of most of theproduct of Example 9 afforded3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl-5 or6-aminophthalide (I: X ═ (CH₃)₂ N, Y² ═ CH₃, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁷═ H, Z⁵ or Z⁶ ═ H₂ N and the other of Z⁵ or Z⁶ ═ H) or a mixture ofboth.

When applied to silica gel3-(2,4-bis(dimethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-5or 6-aminophthalide formed a gray-violet or gray-black image which wasxerographically copiable.

EXAMPLE 12

A. A mixture of 4-(dimethylamino)phthalic anhydride (7 g.),N,N-dimethylaniline (9.12 g.), aluminum chloride (11.7 g.) and benzene(36.5 ml.) was stirred (for 10 min.) at ice-bath temperature, thenovernight at room temperature. The mixture was then extracted withdilute sulfuric acid (20%, 80 ml.). Adjustment of the pH of the acidicextract to 5 afforded a mixture of2-(4-(dimethylamino)benzoyl)-4-(dimethylamino)benzoic acid (IV: Y² ═ Z⁴═ Z"⁶ ═ Z⁷ ═ H, Y'⁴ ═ Z"⁵ ═ (CH₃)₂ N) and2-(4-(dimethylamino)benzoyl)-5-(dimethylamino)benzoic acid (IV: Y² ═ Z⁴═ Z"⁵ ═ Z⁷ ═ H, Y'⁴ ═ Z"⁶ ═ (CH₃)₂ N) (6.3 g.).

B. A mixture of part (3.12 g.) of the mixture of products from part A ofthis example, N,N,N',N'-tetramethyl-m-phenylenediamine (1.5 g.) andacetic anhydride (20 g.) was heated (to 85° C.), then cooled. Theresulting precipitate was washed with ether, washed with alkali andrecrystallized from acetone, affording3-(2,4-bis(dimethylamino)phenyl-3-(4-(dimethylamino)phenyl)-5-(dimethylamino)phthalide(I: X ═ Y⁴ ═ Z⁵ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁶ ═ Z⁷ ═ H) (m.p. 222°-225° C.).

When applied to acidic clay3-(2,4-bis(dimethylamino)-phenyl)-3-(4-dimethylamino)phenyl)-5-(dimethylamino)phthalideslowly formed a blue-gray image which was xerographically copiable.

C. The acetic anhydride filtrate from part B of this example was treatedfirst with dilute hydrochloric acid (16 g. of concentrated acid plus 80g. of water), then basified, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-dimethylamino)phenyl)-6-(dimethylamino)phthalide(I: X ═ Y⁴ ═ Z⁶ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁷ ═ H) (m.p. 182°-185° C.after purification).

When applied to acidic clay3-(2,4-bis(dimethylamino)phenyl)-3-(4-dimethylamino)phenyl)-6-(dimethylamino)phthaliderapidly formed a violet-purple image which was xerographically copiable.

D. Propionic anhydride, phosphorus oxychloride or thionyl chloride canbe substituted for acetic anhydride in part B of this example.

EXAMPLE 13

A. A mixture of 4-(dimethylamino)phthalic anhydride (1.91 g.),N,N,N',N'-tetramethyl-m-phenylenediamine (1.64 g.), zinc chloride (2.70g.) and chlorobenzene (50 ml.) was heated under reflux during two hours.The chlorobenzene layer was decanted and the residue was slurried inwater (80 ml.) and dilute hydrochloric acid (10%, 4 drops), affording2-(2,4-bis(dimethylamino)benzoyl)-4-(dimethylamino)benzoic acid (II: Y'²═ Y'⁴ ═ Z'⁵ ═ (CH₃)₂ N, Z⁴ ═ Z'⁶ ═ Z⁷ ═ H) (m.p. 216°-222° C.) or the5-(dimethylamino) isomer thereof.

B. A mixture of2-(2,4-bis(dimethylamino)benzoyl)-4-(dimethylamino)benzoic acid or the5-(dimethylamino) isomer thereof (10 g.),N,N,N'-tetramethyl-m-phenylenediamine (2.30 g.) and acetic anhydride (50ml.) was warmed (at 30°-35° C.) during 1 hour. MoreN,N,N',N'-tetramethyl-m-phenylenediamine (1.15 g.) was added and warmingwas continued. The mixture was diluted with dilute hydrochloric acid(10%) and ice and filtered. The filtrate was made alkaline.Crystallization of the product from toluene afforded3,3-bis(2,4-bis(dimethylamino)phenyl)-5-(dimethylamino)phthalide (I: X ═Y² ═ Y⁴ ═ Z⁵ ═ (CH₃)₂ N, Z⁴ ═ Z⁶ ═ Z⁷ ═ H) (m.p. 188°-192° C.) or the6-(dimethylamino) isomer thereof.

C. Substituting N-ethyl-N-(4-hydroxybutyl)aniline forN,N,N',N'-tetramethyl-m-phenylenediamine in part B of this example anddeacetylating the resulting product, there is obtained3-(2,4-bis(dimethylamino)phenyl)-3-(4-(ethyl-(4-hydroxybutyl)amino)phenyl)-5-(dimethylamino)phthalide(I: X ═ Z⁵ ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁶ ═ Z⁷ ═ H, Y⁴ ═ CH₃ CH₂ (HO(CH₂)₄)N)or the 6-(dimethylamino) isomer thereof.

D. Substituting 4-methylphthalic anhydride, 4-nitrophthalic anhydride or4-chlorophthalic anhydride for 4-(dimethylamino)phthalic anhydride inpart A of this example, there are obtained, respectively,2-(2,4-bis(dimethylamino)benzoyl)-5-methylbenzoic acid (VI: X ═ (CH₃)₂N, Z⁴ ═ Z"⁵ ═ Z⁷ ═ H, Z"⁶ ═ CH₃),2-(2,4-bis(dimethylamino)benzoyl)-5-nitrobenzoic acid (VI: X ═ (CH₃)₂ N,Z⁴ ═ Z'⁵ ═ Z⁷ ═ H, Z'⁶ ═ O₂ N) and2-(2,4-bis(dimethylamino)benzoyl-5-chlorobenzoic acid (VI: X ═ (CH₃)₂ N,Z⁴ ═ Z'⁵ ═ Z⁷ ═ H, Z'⁶ ═ Cl).

E. Substituting 2-(2,4-bis(dimethylamino)benzoyl)-5-methylbenzoic acid,2-(2,4-bis(dimethylamino)benzoyl)-5-nitrobenzoic acid or2-(2,4-bis(dimethylamino)benzoyl)-5-chlorobenzoic acid for2-(2,4-bis(dimethylamino)benzoyl)-5-(dimethylamino)benzoic acid in partB of this example, there are obtained, respectively,3,3-bis(2,4-bis(dimethylamino)phenyl)-6-methylphthalide (I: X ═ Y² ═ Y⁴═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ CH₃) and3,3-bis(2,4-bis(dimethylamino)phenyl)-6-nitrophthalide (I: X ═ Y² ═ Y⁴ ═(CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ O₂ N) and3,3bis(2,4-bis(dimethylamino)phenyl)-6-chlorophthalide (I: X ═ Y² ═ Y⁴ ═(CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ Cl).

EXAMPLE 14

Sodium nitrite is added to a mixture of3,3-bis(2,4-bis(dimethylamino)phenyl)-6-aminophthalide in dilutehydrobromic acid. The resulting mixture is added to a solution ofcuprous bromide in dilute hydrobromic acid, affording, afterbasification, 3,3-bis(2,4-bis(dimethylamino)phenyl)-6-bromophthalide (I:X ═ Y² ═ Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁷ ═ H, Z⁶ ═ Br).

EXAMPLE 15

A. A mixture of phthalic anhydride (30 g.), N,N-diethylaniline (71.6g.), aluminum chloride (60 g.) and o-dichlorobenzene (200 ml.) washeated (to 75° C.), then diluted with ice (300 ml.) and water (500 ml.).The o-dichlorobenzene layer was separated and steam distilled. Additionof base to a solution of the residue in dilute sulfuric acid afforded2-(4-diethylamino)benzoyl)benzoic acid (IV: Y² ═ Z⁴ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ H,Y'⁴ ═ (CH₃ CH₂)₂ N) (58.9 g., m.p. 179°-181° C.).

B. A mixture of 2-(4-diethylamino)benzoyl)benzoic acid (5.94 g.),N,N,N',N'-tetramethyl-m-phenylenediamine (3.61 g.) and acetic anhydride(3 ml.) was warmed (to 45° C.). Addition of methanol (20 ml.) afforded3-(2,4-bis(dimethylamino)phenyl)-3-(4-(diethylamino)phenyl)phthalide I:X ═ (CH₃)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H, Y⁴ ═ (CH₃ CH₂)₂ N) (6.8 g.,m.p. 168°-169.5° C.).

EXAMPLE 16

A mixture of 2-(4-dimethylamino)benzoyl)benzoic acid (8.07 g.),N,N,N',N'-tetraethyl-m-phenylenediamine (7.26 g.) and acetic anhydride(5 ml.) was heated (at 52° C.) during one and one-half hours. Additionof methanol (10 ml., then 15 ml.) afforded3-(2,4-bis(diethylamino)phenyl)-3-(4-dimethylamino)phenyl)phthalide (I:X ═ (CH₃ CH₂)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H, Y⁴ ═ (CH₃)₂ N) (10.92 g.,m.p. 117°-119° C.).

EXAMPLE 17

A mixture of 2-(4-diethylamino)benzoyl)benzoic acid (5.94 g.),N,N,N',N'-tetraethyl-m-phenylenediamine (4.84 g.) and acetic anhydride(3 ml.) was heated at 70° C. Addition of methanol (20 ml.) afforded3-(2,4-bis(diethylamino)phenyl)-3-(4-(diethylamino)phenyl)phthalide (I:X ═ Y⁴ ═ (CH₃ CH₂)₂ N, Y² ═ Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (7.1 g., 135°-137°C.).

EXAMPLE 18

A mixture of 2-(2-methyl-4-(diethylamino)benzoyl)benzoic acid (12.48g.), N,N,N',N'-tetraethyl-m-phenylenediamine (10.56 g.) and aceticanhydride (12 ml.) was warmed (at 40±8° C.) during one hour, dilutedwith water (50 ml., then 100 ml.), adjusted to pH 4.6 and filtered. Thefiltrate was clarified with water and adjusted to pH 5.5.Recrystallization of the resulting product (m.p. 134°-140° C.) frommethanol afforded3-(2,4-bis(diethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃ CH₂)₂ N, Y² ═ CH₃, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (m.p.149°-151° C.).

EXAMPLE 19

A. A mixture of tetrachlorophthalic anhydride (42.8 g.),N,N-dimethylaniline (61 g.), aluminum chloride (60 g.) and chlorobenzene(180 ml.) was heated (to 75° C.) during one and one-half hours, thendiluted with ice-water (500 ml.). The chlorobenzene layer was separatedand steam distilled. The residue was heated (to 95° C.) with dilutesulfuric acid (50%, 250 ml.) and cooled, affording2-(4-(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid (IV: Y² ═H, Y'⁴ ═ (CH₃)₂, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ Cl) (57.4 g., m.p. 216°-217° C.).

B. A mixture of 2-(4-(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoicacid (20.3 g.), N,N,N',N'-tetramethyl-m-phenylenediamine (88%, 9.3 g.)and acetic anhydride (74 ml.) was heated (to 95° C.) during one hour,then cooled, affording3-(2,4-bis(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-4,5,6,7-tetrachlorophthalide(I: X ═ Y⁴ ═ (CH₃)₂ N, Y² ═ H, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl) (20.3 g., m.p.227°-229° C.).

EXAMPLE 20

A. A mixture of tetrachlorophthalic anhydride (42.8 g.),N,N-diethylaniline (74 g.), aluminum chloride (60 g.) and chlorobenzene(180 ml.) was heated (to 75° C.) during one and one-half hours, thendiluted with ice-water (500 ml.). The chlorobenzene layer was separatedand steam distilled. Addition of sodium hydroxide solution (50%) to asolution of the residue in dilute sulfuric acid (50%, 250 ml.) afforded2-(4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid (IV: Y² ═ H,Y'⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z"⁵ ═ Z"⁶ ═ Z⁷ ═ Cl) (59 g., m.p. 228°-233°C.).

B. A mixture of 2-(4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoicacid (8.70 g.), N,N,N',N'-tetramethyl-m-phenylenediamine (3.61 g.) andacetic anhydride (5 ml.) was heated (to 90° C.). Addition of methanol(10 ml.) and slurrying the resulting product with methanol afforded3-(2,4-bis(dimethylamino)phenyl)-3-(4-diethylamino)phenyl)-4,5,6,7-tetrachlorophthalide(I: X ═ (CH₃)₂ N, Y² ═ H, Y⁴ ═ (CH₃ CH₂)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl)(5.60 g., m.p. 206°-207.5° C.).

EXAMPLE 21

A mixture of 2-(4-(dimethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoicacid (16.28 g.), N,N,N',N'-tetraethyl-m-phenylenediamine (9.68 g.) andacetic anhydride (10 ml.) was heated (at 91° C.) during 2 hours.Addition of methanol (20 ml., then 12 ml., then 10 ml.) afforded3-(2,4-bis-(diethylamino)phenyl)-3-(4-dimethylamino)phenyl)-4,5,6,7-tetrachlorophthalide(I: X ═ (CH₃ CH₂)₂ N, Y² ═ H, Y⁴ ═ (CH₃)₂ N, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl) inthree fractions (m.p. 174°-176° C., m.p. 180°-181° C. and m.p. 180°-181°C.).

EXAMPLE 22

A mixture of 2-(4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid(8.70 g.), N,N,N',N'-tetraethyl-m-phenylenediamine (4.85 g.) and aceticanhydride (5 ml.) was heated (to 90° C.). Addition of methanol (10 ml.)and slurrying the resulting product with methanol (20 ml.) afforded3-(2,4-bis(diethylamino)phenyl)-3-(4-(diethylamino)-phenyl)-4,5,6,7-tetrachlorophthalide(I: X ═ Y⁴ ═ (CH₃ CH₂)₂ N, Y² ═ H, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl) (7.85 g.,m.p. 196°-197° C.).

EXAMPLE 23

A mixture of2-(2-methyl-4-(diethylamino)benzoyl)-3,4,5,6-tetrachlorobenzoic acid(44.9 g.), N,N,N',N'-tetraethyl-m-phenylenediamine (29.7 g.) and aceticanhydride (50 ml.) was heated (at 85°-90° C.) during 3 hours. Theresulting crystalline product was washed with methanol, slurried in hotethanol and washed again with methanol, affording3-(2,4-bis(diethylamino)phenyl)-3-(2-methyl-4-(diethylamino)phenyl)-4,5,6,7-tetrachlorophthalide(I: X ═ Y⁴ ═ (CH₃ CH₂)₂ N, Y² ═ CH₃, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ Cl) (34.1 g.,m.p. 162°-164° C.).

EXAMPLE 24

A. A mixture of phthalic anhydride (11.2 g.),N,N-diethyl-m-chloroaniline (28.2 g.), aluminum chloride (30 g.) andchlorobenzene (75 ml.) was heated (to 90° C.), then diluted with water(300 ml.). The chlorobenzene layer was separated and steam distilled.Adjustment of the pH of the aqueous residue to about 3 afforded2-(2-chloro-4-(diethylamino)-benzoyl)benzoic acid (II: Y'² ═ Cl, Y'⁴ ═(CH₃ CH₂)₂ N, Z⁴ ═ Z'⁵ ═ Z'⁶ ═ Z⁷ ═ H) (15.9 g., m.p. 140°-144° C.).

B. A mixture of 2-(2-chloro-4-(diethylamino)benzoyl)-benzoic acid (6.61g.), N,N,N',N'-tetraethyl-m-phenylenediamine (4.30 g.) and aceticanhydride (5 ml.) was allowed to stand overnight at room temperature,then diluted with methanol (10 ml.), affording3-(2,4-bis(diethylamino)phenyl)-3-(2-chloro-4-(diethylamino)phenyl)phthalide(I: X ═ Y⁴ ═ (CH₃ CH₂)₂ N, Y² ═ Cl, Z⁴ ═ Z⁵ ═ Z⁶ ═ Z⁷ ═ H) (3.94 g.,m.p. 141°-143° C.).

By methods similar to those described in the foregoing examples thefollowing additional 2-benzoylbenzoic acids of Formula IV (Table I) and3,3-diphenylphthalides of Formula I (Table II) were prepared or can beprepared.

                                      Table I                                     __________________________________________________________________________    2-Benzoylbenzoic Acids                                                        Example                                                                            Y.sup.2                                                                              Y'.sup.4    Z.sup.4                                                                          Z".sup.5                                                                         Z".sup.6                                                                         Z.sup.7                                                                          M.p.(° C.)                                                                    % Yield                            __________________________________________________________________________     25A  H                                                                                    ##STR17##   Cl                                                                               Cl                                                                               Cl                                                                               Cl                                                                               222-225                                                                              12                                 26A  H                                                                                    ##STR18##   H  H  H  H  104-107                                                                              83                                28A  CH.sub.3                                                                             (CH.sub.3 CH.sub.2).sub.2 N                                                               H.sub.2 Cl.sub.2                                                                          199-206                                                                              68                                 29A  CH.sub.3                                                                             (CH.sub.3 CH.sub.2).sub.2 N                                                               Br Br Br Br 202-205                                                                              91                                 30A  H      (CH.sub.3 CH.sub.2)(C.sub.6 H.sub.5 CH.sub.2 N                                            Cl Cl Cl Cl 116-132                                   32A  CH.sub.3                                                                             (CH.sub.3).sub.2 N                                                                        H  H  H  H  106-110                                                                              64                                 33A  (CH.sub.3 CH.sub.2).sub.2 N                                                          (CH.sub.3 CH.sub.2).sub.2 N                                                               Cl Cl Cl Cl 174-178                                   35A  H      (CH.sub.3 CH.sub.2)(C.sub.6 H.sub.5 CH.sub.2)N                                            H  H  H  H  197-200                                                                              39                                  36A  H                                                                                    ##STR19##   Cl                                                                               Cl                                                                               Cl                                                                               Cl                                                                               100-102                                                                              69                                 37A  CH.sub.3                                                                             ##STR20##   Cl                                                                               Cl                                                                               Cl                                                                               Cl                                                                               58-66  84                                 38A  H                                                                                    ##STR21##   H  H  H  H  110-120                                                                              22                                40A  H      CH.sub.3 (4-CH.sub.3 OC.sub.6 H.sub.4)N                                                   H  H  H  H  235-242                                                                              30                                 41A  H      CH.sub.3 (4-CH.sub.3 OC.sub.6 H.sub.4)N                                                   Cl Cl Cl Cl 128-130                                                                              66                                  42A  CH.sub.3                                                                             ##STR22##   H  H  H  H  183-187                                                                              80                                 43A  H                                                                                    ##STR23##   H  H  H  H  200 dec.                                                                             71                                45A  (CH.sub.3 CH.sub.2).sub.2 N                                                          (CH.sub.3 CH.sub.2).sub.2 N                                                               H  H  H  H  189-190                                                                              17                                 __________________________________________________________________________

                                      Table II                                    __________________________________________________________________________    3,3-Diphenylphthalides                                                        Example                                                                            X      Y.sup.2                                                                              Y.sup.4     Z.sup.4                                                                         Z.sup.5                                                                         Z.sup.6                                                                            Z.sup.7                                                                         M.p.(° C.)                                                                    % Yield                      __________________________________________________________________________     25B  (CH.sub.3).sub.2 N                                                                   H                                                                                    ##STR24##   Cl                                                                              Cl                                                                              Cl   Cl                                                                              250-251                                                                              20                           26B  (CH.sub.3).sub.2 N                                                                   H                                                                                    ##STR25##   H                                                                               H                                                                               H    H                                                                               208-210                                                                              64                           27   (CH.sub.3 CH.sub.2).sub.2 N                                                          H                                                                                    ##STR26##   H                                                                               H                                                                               H    H                                                                               157-158                                                                              96                          28B  (CH.sub.3 CH.sub.2).sub.2 N                                                          CH.sub.3                                                                             (CH.sub.3 CH.sub.2).sub.2 N                                                               H.sub.2 Cl.sub.2                                                                         169-172                                                                              18                           29B  (CH.sub.3).sub.2 N                                                                   CH.sub.3                                                                             (CH.sub.3 CH.sub.2).sub.2 N                                                               Br                                                                              Br                                                                              Br   Br                                                                              245-246                                                                              51                           30B  (CH.sub.3).sub.2 N                                                                   H      (CH.sub.3 CH.sub.2)(C.sub.6 H.sub.5 CH.sub.2)N                                            Cl                                                                              Cl                                                                              Cl   Cl                                                                              180-182                                                                              26                            31   (CH.sub.3).sub.2 N                                                                   H                                                                                    ##STR27##   H                                                                               H                                                                               (CH.sub.3).sub.2 N                                                                 H                                                                               128-130                            32B  (CH.sub.3).sub.2 N                                                                   CH.sub.3                                                                             (CH.sub.3).sub.2 N                                                                        H H H    H 224-228                                                                              64                           33B  (CH.sub.3).sub.2 N                                                                   (CH.sub.3 CH.sub.2).sub.2 N                                                          (CH.sub.3 CH.sub.2).sub.2 N                                                               Cl                                                                              Cl                                                                              Cl   Cl                                                                              132-135                             34   (CH.sub.3).sub.2 N                                                                   CH.sub.3                                                                             (CH.sub.3 CH.sub.2).sub.2 N                                                               H.sub.2 Cl.sub.2                                                                         186-192                                                                              32                           35B  (CH.sub.3).sub.2 N                                                                   H      (CH.sub.3 CH.sub.2)(C.sub.6 H.sub.5 CH.sub.2)N                                            H H H    H 130-132                                                                              98                            36B  (CH.sub.3).sub.2 N                                                                   H                                                                                    ##STR28##   Cl                                                                               Cl                                                                             Cl   Cl                                                                              276-279                                                                              43                           37B  (CH.sub.3).sub.2 N                                                                   CH.sub.3                                                                             ##STR29##   Cl                                                                              Cl                                                                              Cl   Cl                                                                              245-249                                                                              56                           38B  (CH.sub.3).sub.2 N                                                                   H                                                                                    ##STR30##   H                                                                               H                                                                               H    H                                                                               192-194                                                                              68                          39   (CH.sub.3 CH.sub.2).sub.2 N                                                          H      (CH.sub.3).sub.2 N                                                                        H H (CH.sub.3).sub.2 N                                                                 H 68-72  74                           40B  (CH.sub.3).sub.2 N                                                                   H      CH.sub.3 (4-CH.sub. 3 OC.sub.6 H.sub.4)N                                                  H H H    H 155-158                             41B  (CH.sub.3).sub.2 N                                                                   H      CH.sub.3 (4-CH.sub. 3 OC.sub.6 H.sub.4)N                                                  Cl                                                                              Cl                                                                              Cl   Cl                                                                              254-256                                                                              21                            42B  (CH.sub.3).sub.2 N                                                                   CH.sub.3                                                                             ##STR31##   H                                                                               H                                                                               H    H                                                                               244-247                                                                              59                           43B  (CH.sub.3).sub.2 N                                                                   H                                                                                    ##STR32##   H                                                                               H                                                                               H    H                                                                               192-194                                                                              63                           44                                                                                 ##STR33##                                                                            CH.sub.3                                                                             (CH.sub.3 CH.sub.2).sub.2 N                                                               H                                                                               H                                                                               H    H                                                                               163-165                                                                              16                          45B  (CH.sub.3 CH.sub.2).sub.2 N                                                          (CH.sub.3 CH.sub.2).sub.2 N                                                          (CH.sub.3 CH.sub.2).sub.2 N                                                               H H H    H 149-151                                                                              33                           46   (CH.sub.3 CH.sub.2).sub.2 N                                                          H      (CH.sub.3 CH.sub.2)(C.sub.6 H.sub.5 CH.sub.2).sub.N                                       Cl                                                                              Cl                                                                              Cl   Cl                                                                              139-142                                                                              39                           47   (CH.sub.3 CH.sub.2).sub.2 N                                                          (CH.sub.3 CH.sub.2).sub.2 N                                                          (CH.sub.3 CH.sub.2).sub.2 N                                                               Cl                                                                              Cl                                                                              Cl   Cl                                                                              110-117                                                                              27                            48                                                                                 ##STR34##                                                                            CH.sub.3                                                                             (CH.sub.3 CH.sub.2).sub.2 N                                                               Cl                                                                              Cl                                                                              Cl   Cl                                                                              135-137                                                                              84                          __________________________________________________________________________

EXAMPLE 49

3-(2,4-Bis(dimethylamino)phenyl)-3-(2-methyl-4-diethylamino)phenyl)phthalide(Example 2B) and3-(2,4-bis-(dimethylamino)phenyl)-3-(4-(dimethylamino)phenyl)-6-(dimethylamino)phthalide(Example 12C) were microencapsulated as follows. A solution of the colorprecursor (1.46 g.) in isopropylbiphenyl (60 g.) and a solution ofcarboxymethylcellulose (5 g.) in water (200 ml.) were mixed andemulsified by rapid stirring. The desired particle size (5 microns) waschecked by microscope. To the emulsion was added a solution of pigskingelatin (15 g.) in water (120 ml.). The pH was adjusted to 6.5 withaqueous sodium hydroxide (10%) with rapid stirring. Water (670 ml.) wasadded slowly with heating (at 50° C.). The pH was adjusted to 4.5 withaqueous acetic acid (10%) with continued rapid stirring (5 min.).Aqueous glutaraldehyde (10 g., 25%) was added with continued rapidstirring (15 min.).

The microcapsule mixture was stirred more slowly overnight, diluted withwater (to 1120 g.), and coated onto white typewriter paper sheets(0.0015 in. film thickness). The sheets were air dried. Duplicatetypewritten images were made on four types of receiving sheets, threecoated with phenolic resins and one coated with acid clay. The colorprecursor of Example 2B produced blue-black images on the receivingsheets coated with phenolic resins and a brown image on the receivingsheets coated with acidic clay. The color precursor of Example 12Cproduced deep purple images on the receiving sheets coated with phenolicresins and a blue-black image on the receiving sheet coated with acidicclay.

EXAMPLE 50

Polyvinyl alcohol dispersions of the color precursors of Example 2B (2.0g.) and Example 12C (2.0 g.) were prepared by shaking with water (3.7g.), aqueous polyvinyl alcohol (10%, 8.6 g.) and zirconium grindingbeads (10 g.). A polyvinyl alcohol dispersion of bisphenol A (9.8 g.)was prepared by shaking with water (18.2 g.), aqueous polyvinyl alcohol(10%, 42 g.) and zirconium grinding beads (70 ml.). A mixture of each ofthe color precursor dispersions (2.1 g. of each) and the bisphenol Adispersion (47.9 g.) was made by thorough mixing. Each mixture wascoated (at thicknesses of 0.003 in. and 0.0015 in.) onto white mimeopaper sheets and the sheets were dried at room temperature. Contactingthe coated sheets with a heated stylus (150° C.) produced a blue-blackimage on the sheet coated with the color precursor of Example 2B and adeep purple image on the sheet coated with the color precursor ofExample 12C.

We claim:
 1. 3-(2-X-4-X-Phenyl)-3-(2-Y² -4-Y⁴ -phenyl)-4-Z⁴ -5-Z⁵ -6-Z⁶-7-Z⁷ -phthalide of the formula ##STR35## wherein: X is dialkylaminowherein alkyl is non-tertiary alkyl of one to four carbon atoms;Y² ishydrogen, non-tertiary alkyl of one to four carbon atoms, dialkylaminowherein alkyl is non-tertiary alkyl of one to four carbon atoms,alkanoylamino of two to five carbon atoms, non-tertiary alkoxy of one tofour carbon atoms or halo; Y⁴ is the same as Y² when Y² is dialkylamino;or dialkylamino, pyrrolidino, piperidino, alkylbenzylamino,alkyl(4-alkoxyphenyl)amino or alkyl(Q-(CH₂)_(n) -amino, wherein alkyl isnon-tertiary alkyl of one to four carbon atoms, alkoxy is non-tertiaryalkoxy of one to four carbon atoms, Q is hydroxy or chloro and n is twoto four when Y² is other than dialkylamino; Z⁴ is hydrogen or halo; Z⁵is hydrogen or halo; or non-tertiary alkyl of one to four carbon atoms,nitro, amino or dialkylamino wherein alkyl is non-tertiary alkyl of oneto four carbon atoms when Z⁴, Z⁶ and Z⁷ are each hydrogen; Z⁶ ishydrogen or halo; or non-tertiary alkyl of one to four carbon atoms,nitro, amino or dialkylamino wherein alkyl is non-tertiary alkyl of oneto four carbon atoms when Z⁴, Z⁵ and Z⁷ are each hydrogen; and Z⁷ ishydrogen or halo.
 2. A compound according to claim 1 wherein Z⁴, Z⁵, Z⁶,and Z⁷ are each hydrogen.
 3. A compound according to claim 2 wherein Y²is hydrogen.
 4. A compound according to claim 3 wherein Y⁴ isdialkylamino.
 5. A compound according to claim 4 wherein Y⁴ isdimethylamino.
 6. A compound according to claim 5 wherein X isdimethylamino.
 7. A compound according to claim 4 wherein Y⁴ isdiethylamino.
 8. A compound according to claim 7 wherein X isdimethylamino.
 9. A compound according to claim 3 wherein Y⁴ isalkylbenzylamino.
 10. A compound according to claim 9 wherein Y⁴ isethylbenzylamino.
 11. A compound according to claim 10 wherein X isdimethylamino.
 12. A compound according to claim 2 wherein Y² is alkyl.13. A compound according to claim 12 wherein Y² is methyl.
 14. Acompound according to claim 13 wherein Y⁴ is dialkylamino.
 15. Acompound according to claim 14 wherein Y⁴ is dimethylamino.
 16. Acompound according to claim 15 wherein X is dimethylamino.
 17. Acompound according to claim 14 wherein Y⁴ is diethylamino.
 18. Acompound according to claim 17 wherein X is dimethylamino.
 19. Acompound according to claim 1 wherein Z⁴, Z⁵, Z⁶ and Z⁷ are each halo.20. A compound according to claim 19 wherein Z⁴, Z⁵, Z⁶ and Z⁷ are eachchloro.
 21. A compound according to claim 20 wherein Y² is hydrogen. 22.A compound according to claim 21 wherein Y⁴ is dialkylamino.
 23. Acompound according to claim 22 wherein Y⁴ is dimethylamino.
 24. Acompound according to claim 23 wherein X is dimethylamino.
 25. Acompound according to claim 24 wherein Y⁴ is diethylamino.
 26. Acompound according to claim 25 wherein X is dimethylamino.
 27. Acompound according to claim 25 wherein X is diethylamino.
 28. A compoundaccording to claim 20 wherein Y² is alkyl.
 29. A compound according toclaim 28 wherein Y² is methyl.
 30. A compound according to claim 29wherein Y⁴ is dialkylamino.
 31. A compound according to claim 30 whereinY⁴ is diethylamino.
 32. A compound according to claim 31 wherein X isdimethylamino.
 33. A compound according to claim 31 wherein X isdiethylamino.
 34. A compound according to claim 20 wherein Y² isdialkylamino.
 35. A compound according to claim 34 wherein Y² isdimethylamino.
 36. A compound according to claim 35 wherein X isdimethylamino.
 37. A compound according to claim 1 wherein Z⁶ isdialkylamino.
 38. A compound according to claim 37 wherein Z⁶ isdimethylamino.
 39. A compound according to claim 38 wherein Y² ishydrogen.
 40. A compound according to claim 39 wherein Y⁴ isdialkylamino.
 41. A compound according to claim 40 wherein Y⁴ isdimethylamino.
 42. A compound according to claim 41 wherein X isdimethylamino.
 43. The process for preparing 3-(2-X-4-X-phenyl)-3-(2-Y²-4-Y'⁴ -phenyl)-4-Z⁴ -5-Z"⁵ -6-Z"⁶ -7-Z⁷ -phthalide which comprisescondensing 2-(2-Y² -4-Y'⁴ -benzoyl)-3-Z⁴ -4-Z"⁵ -5-Z"⁶ -6-Z⁷ -benzoicacid with 1-X-3-X-benzene in contact with the anhydride of an alkanoicacid of two to five carbon atoms, phosphorus oxychloride or thionylchloride, wherein:X is dialkylamino wherein alkyl is non-tertiary alkylof one to four carbon atoms; Y² is hydrogen, non-tertiary alkyl of oneto four carbon atoms, dialkylamino wherein alkyl is non-tertiary alkylof one to four carbon atoms, alkanoylamino of two to five carbon atoms,non-tertiary alkoxy of one to four carbon atoms or halo; Y'⁴ is the sameas Y² when Y² is dialkylamino; or dialkylamino, pyrrolidino, piperidino,alkylbenzylamino, alkyl(4-alkoxyphenyl)amino oralkyl(Q'-(CH₂)_(n))amino, wherein alkyl is non-tertiary alkyl of one tofour carbon atoms, alkoxy is non-tertiary alkoxy of one to four carbonatoms, Q' is chloro and n is two to four when Y² is other thandialkylamino; Z⁴ is hydrogen or halo; Z"⁵ is hydrogen or halo; ornon-tertiary alkyl of one to four carbon atoms, nitro, dialkylaminowherein alkyl is non-tertiary alkyl of one to four carbon atoms when Z⁴,Z"⁶ and Z⁷ are each hydrogen; Z"⁶ is hydrogen or halo; or non-tertiaryalkyl of one to four carbon atoms, nitro, dialkylamino wherein alkyl isnon-tertiary alkyl of one to four carbon atoms when Z⁴, Z"⁵ and Z⁷ areeach hydrogen; and Z⁷ is hydrogen or halo.
 44. The process for preparing3-(2-X-4-X-phenyl)-3-(2-Y² -4-Y'⁴ -phenyl)-4-Z⁴ -5-Z"⁵ -6-Z"⁶ -7-Z⁷-phthalide which comprises condensing 2-(2-X-4-X-benzoyl)-3-Z⁴ -Z"⁵-5-Z"⁶ -6-Z⁷ -benzoic acid with 1-Y² -3-Y'⁴ -benzene in contact with theanhydride of an alkanoic acid of two to five carbon atoms, phosphorusoxychloride or thionyl chloride, wherein:X is dialkylamino wherein alkylis non-tertiary alkyl of one to four carbon atoms; Y² is hydrogen,non-tertiary alkyl of one to four carbon atoms, dialkylamino whereinalkyl is non-tertiary alkyl of one to four carbon atoms, alkanoylaminoof two to five carbon atoms, non-tertiary alkoxy of one to four carbonatoms or halo; Y'⁴ is the same as Y² when Y² is dialkylamino; ordialkylamino, pyrrolidino, piperidino, alkylbenzylamino,alkyl(4-alkoxyphenyl)amino or alkyl(Q'-(CH₂)_(n))amino, wherein alkyl isnon-tertiary alkyl of one to four carbon atoms, alkoxy is non-tertiaryalkoxy of one to four carbon atoms, Q' is chloro and n is two to fourwhen Y² is other than dialkylamino; Z⁴ is hydrogen or halo; Z"⁵ ishydrogen or halo; or non-tertiary alkyl of one to four carbon atoms,nitro, dialkylamino wherein alkyl is non-tertiary alkyl of one to fourcarbon atoms when Z⁴, Z"⁶ and Z⁷ are each hydrogen; Z"⁶ is hydrogen orhalo; or non-tertiary alkyl of one to four carbon atoms, nitro,dialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms when Z⁴, Z"⁵ and Z⁷ are each hydrogen; and Z⁷ is hydrogen or halo.45. 3-(2-X-4-X-Phenyl)-3-(2Y² -4-Y⁴ -phenyl)-4-Z⁴ -5-Z⁵ -6-Z⁶ -7-Z⁷-phthalide according to claim 1 wherein:X is dialkylamino wherein alkylis non-tertiary alkyl of one to four carbon atoms; Y² is hydrogen,non-tertiary alkyl of one to four carbon atoms, alkanoylamino of two tofive carbon atoms, non-tertiary alkoxy of one to four carbon atoms orhalo; Y⁴ is pyrrolidino; Z⁴ is hydrogen or halo; Z⁵ is hydrogen or halo;or non-tertiary alkyl of one to four carbon atoms, nitro, amino ordialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms when Z⁴, Z⁶ and Z⁷ are each hydrogen; Z⁶ is hydrogen or halo; ornon-tertiary alkyl of one to four carbon atoms, nitro, amino ordialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms when Z⁴, Z⁵ and Z⁷ are each hydrogen; and Z⁷ is hydrogen or halo.46. A compound according to claim 45 wherein Z⁴, Z⁵, Z⁶ and Z⁷ are eachhydrogen.
 47. A compound according to claim 46 wherein Y² is hydrogen.48. A compound according to claim 47 wherein X is dimethylamino. 49.3-(2-X-4-X-Phenyl)-3-(2-Y² -4-Y⁴ -phenyl)-4-Z⁴ -5-Z⁵ -6-Z⁶ -7-Z⁷-phthalide according to claim 1 wherein:X is dialkylamino wherein alkylis non-tertiary alkyl of one to four carbon atoms; Y² is hydrogen,non-tertiary alkyl of one to four carbon atoms, alkanoylamino of two tofive carbon atoms, non-tertiary alkoxy of one to four carbon atoms orhalo; Y⁴ is piperidino; Z⁴ is hydrogen or halo; Z⁵ is hydrogen or halo;or non-tertiary alkyl of one to four carbon atoms, nitro, amino ordialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms when Z⁴, Z⁶ and Z⁷ are each hydrogen; Z⁶ is hydrogen or halo; ornon-tertiary alkyl of one to four carbon atoms, nitro, amino ordialkylamino wherein alkyl is non-tertiary alkyl of one to four carbonatoms when Z⁴, Z⁵ and Z⁷ are each hydrogen; and Z⁷ is hydrogen or halo.50. A compound according to claim 49 wherein Z⁴, Z⁵, Z⁶ and Z⁷ are eachhydrogen.
 51. A compound according to claim 50 wherein Y² is hydrogen.52. A compound according to claim 51 wherein X is dimethylamino.